InGaN (especially In-rich alloy) has been actively studied for decades since the band gap of InN was revised downward from 2.0 eV to 0.64 eV. The potential applications for alloys of In-rich InGaN hence became apparent. Despite the promising potential, photovoltaic devices based on InGaN have struggled due to a number of key limitations and fundamental physical problems. Firstly, due to the deep excursion of the InN conduction band at the gamma point, defects in InN are almost universally n-type leading to unintentional degenerate doping. This also leads to the problem of electron accumulation at all surfaces and interfaces of InN. Secondly, p-type doping is problematic, partially due to the degenerate doping effect of defects, but it has also been observed that Mg-doping, while leading to a p-type layer, dramatically reduces the quantum efficiency. This thesis explores an alternative approach using n-type InGaN to form a heterojunction with a p-type Si substrate. One potential benefit to using p-type Si as a substrate material for InGaN is that the valence band of Si possibly lines up with the conduction band of InGaN for a specific mole fraction of indium. Such a band alignment is known as a broken gap heterojunction, an example of which is the interface between InAs and Al x Ga 1-x Sb. The benefits of this broken-gap junction include a low series resistance, high electron mobility, and mobility only weakly dependent on temperature. These properties enable new approach to photovoltaic devices. The InGaN/Si heterojunctions were fabricated by plasma-assisted molecular beam epitaxy under stoichiometric flux conditions. An ultra-thin SiN interface layer was introduced, by Si nitridation process, to passivate the substrate surface and prevent In-Si and Ga-Si eutectic problems. InGaN films with a variety of indium mole fractions were grown by calibrating the In/Ga flux ratio during the deposition. The chemical composition of as-grown films was characterized by x-ray diffraction. Subsequently, the selected films with indium mole fraction close to 44% were measured by xray photoemission spectroscopy to determine the valence band offset at the InGaN and Si interface. The XPS measured valence band offset of 1.85 eV showed an excellent agreement with the theoretical prediction (1.83 eV), obtained from the branch point energy model, indicating the formation of broken-gap alignment.